Processes for producing copolytriazole-amides



Patented June 27, 1950 PROCESSES FOR PRODUCING COPOLY- TRIAZO AMIDESJames Wotberspoon Fisher and Edward William Wheatley, Spondon, nearDerby, :England, assignors to Celanese Corporation of America, a

corporation of Delaware No Drawing. Application February 6, 1947, Se-

rial No. 726,964. In. Great 11 Claims. 1

This invention relates to improvements in the production of polymericmaterials, and is more particularly concerned with the production ofpolymers suitable for the formation of filaments, films and plasticmaterials.

U. S. application S. No. 609,031, filed August 4, 1945, describes theproduction of nitrogen-containing polymers from dihydrazides ofdicarboxylic "acids in presence of hydrazine, e. g. preferably at, leastby weight of the dihydrazide, over andabove that combined in thedihydrazide and also describes using dicarboxylic esters and an amountof hydrazine in excess of two moles for each mole of dicarboxylic ester.U. S. application S. No. 662,628, filed April 16, 1946, describes theproduction of such polymers from hydrazine and the dicarboxylic acidsthemselves or their anhydrides, again using more than two moles ofhydrazine. Further, U. S. application S. No. 662,628, filed April 16,1946, describes the production of nitrogen-containing polymers frommixtures of diamides and dihydrazides of dicarboxylic acids with freehydrazine, from dicarboxylic acids, esters or anhydrides'with ammoniaand hydrazine using more than two moles of total base including morethan one mole of hydrazine, from dinitriles of dicarboxylic acids withhydrazine, and from various other combinations of raw materials.Polymers may be produced according to these specifications which possesscharacteristics, including resistance to degenerative hydrolysis byboiling concentrated hydrochloric acid, which indicate that they containthe 1.2.4-triazole nucleus in the main chain of atoms and terminalgroups which are either hydrazide groups or at least after hydrolysingtreatment, carboxyl groups, and these polymers are consequently referredto throughout the present specification as substances containing the1.2.4- triazole nucleus.

The polymers obtained are extraordinarily resistant to hydrolys-ingagencies such as boiling hydrochloric acid. Presumably the terminalgroups of the polymers contain some residual hydrazide or some residual.amide groups. Possibly some of the terminal groups are acid hydrazide oramide groups and some are free carboxylic acid groups. Hydrolysis withhydrochloric acid or similar agencies probably converts all the terminalgroups to carboxylic acid groups, but does not apparently break down thepolymer since the intrinsic viscosila after hydrolysis is substantiallythe same as before.

' We have now foundthat the polymers obtained Britain February capableof being iurther condensed with. amideiorming bifunctional monomericreagents and with linear polyamides to give valuable linear polymerswhich it of sufliciently high molecular weight are capable of being spuninto fibre or are of value for other purposes to which polymers are nowapplied. such as the production of films, plastic materials, lacquersand the like.

According to the invention, therefore, synthetic linear condensationpolymers areproduced by a process which comprises reacting a linearpolymer containing the 1.2.4-triazole nucleus and obtainable bycondensation of a hydrazide of a dicarboxylic acid, with a bifunctionalamideforming substance containing a functional group which iscomplementary to a terminal group of said polymer. It is to beunderstood that two groups are complementary in the sense of the presentspecification, when they react with each other to form an amide group.For the purposes of the present invention, particularly importantpolymers containing the triazole nucleus are those produced according tothe processes of U. S. application S. No. 662,628, filed April 16, 1946,and U. S. application S. No. 609,031, filed August 4, 1945, especiallythose containing the 4-amino- 1.2.4-triazole nucleus.

As pointed out in said applications, polymers containing the triazolenucleus may be obtained by heating a reaction mixture which on completehydrolysis contains a. mixture of a dicarboxylic acid free from reactivegroups other than the carboxy groups and a base which is hydrazine or amixture of hydrazine and ammonia. when the base is hydrazine, there ispresent more than 2 moles of hydrazine for each mole of dicarboxylicacid, the excess of hydrazine above 2 moles for each mole ofdicarboxylic acid being in an amount suiiicient to produce a polymerresistant to hydrolysis by hydrochloric acid. Similarly, when the baseis a mixture of hydrazine and ammonia, there is present more than 2moles of hydrazine and ammonia together for each mole of dicarboxylicacid and more than 1 mole of hydrazine for each mole of dicarboxylicacid, the excess of hydrazine and ammonia above 2 moles. for each moleof dicarboxylic acid and the excess of hydrazine above 1 mole for eachmole of dicarboxylic acid being in an amount sufiicient to produce apolymer resistant to hydrolysis by hydrochloric acid.

The process of the invention may be applied to polymers containing thetriazole nucleus which have degrees of polymerisation ranging from. 2

as described in the said prior specifications are 5 up to valuescorresponding, for example, to in- 3 trinsic viscosities of 0.7, 0.9 oreven higher, but it is of mostdmportance in relation to low polymers ofthis type. c. g. those of intrinsic viscosity up to about 0.2-0.3.Reference is made to the prior specifications referred to above fordetails of methods by which such polymers may be pro-' duced. Productsof very low degree of polymerin the meaning of the term polymer asemployed in this specification. Other triazole dicarboxylic acids of thegeneral formula HOOCB'.T.R".CO0H

where T is a 1.2.4-triazole nucleus and R and R" are divalent organicradicles, preferably hydrocarbon, e. g. alkylene, radicles, may also beemployed.

The polymers containing the triazole nucleus obtained directly bycondensation of a dicarboxylic acid dihydrazide or' by an equivalentprocess and having terminal hydrazide groups may be condensed withsuitable monomeric bifunctional amide-forming reagents, for exampledlamines containing at least one hydrogen atom attached to each nitrogenatom of the amino groups, dicarboxylic acids or amide-formingderivatives thereof, amino-carboxylic acids, or mixtures of thesesubstances. Instead of or in addition to monomeric reagents, there maybe employed polymeric bifunctional amide-forming reagents, e. 3. linearpolyamides having terminal amideforming groups. For example, thepolymers containing the triazole nucleus may be condensed with a polymerproduced from a diprimary diamine and a dicarboxylic acid, the terminalups being amino g oups or carboxylic acid groups according to thecomponent, if any, which is used in excess. Such polyamides are alsopreferably of low degree of polymrisation, i. e. they do not possesssfibre-forming properties, and

may, for example, be such as are produced by the condensation of onemolecular proportion of a diamine with two molecular proportions of adicarboxylic acid.

It is found that during the polymerisation, when the polymer containingthe triazole nucleus is one containing terminal hydrazide groups, theoriginal polymer itself may undergo further condensation to produce atrlazole polymer of higher molecular weight than the starting material.This is shown by taking the resulting copolyamide-triazole and boilingit with hydrochloric acid so as to hydrolyse the amide groups present.There is thus obtained a water-insoluble hydrochloride of a triazolepolymer without any amide linkages, and it is found that this polymermay have a higher intrinsic viscosity than the polymeric startingmaterial, thus indicating further polymerisation of the original polymerduring the heating with the bifunctional amide-forming reent.

The proportion of amino groups to carboxylic or equivalent groups in thebifunctional amide- !orming substances which are to be condensed withthepolymer containing the triazole nucleus may vary considerably. Thuswe may condense a poly-aminotriazole with the salt of a diprimarydiamine and a dicarboxylic acid which contains amino and carboxy groupsin substantially equal proportions, or we may have present an excess ofcarboxylic acid groups or an excess of amino groups. Thus, for instance,the polyaminotriazole may be condensed with a body of the approximateconstitution of 2 moles of dicarboxylic acid to 1 mole of diamine, or itmay be condensed with a body of the approximate constitution of 2 molesof diamine to 1 mole of dicarboxylic acid. By starting with a polymercontaining the triazole nucleus in which the terminal groups have beencompletely hydrolysed to carboxylic acid groups, we may condense it witha diamine alone, with a mixture of any proportion of diamine todicarboxylic acid in which the diamine is in excess or is justequivalent to the dicarboxylic acid or with a linear polyamide havingterminal amino groups. Again we may vary the total proportion ofbifunctional amide-forming substances to the proportion of startingpolymer containing the triazole nucleus. By these means a wide varietyof polymers may be produced, and starting with any one polymercontaining the triazole nucleus a range of melting points and otherproperties is attainable. From the point of view of moisture regain inthe products, desirable proportion of polymer containing the triazolenucleus to bifunctional amide-forming substance lie between 40:60 and80:20.

As suitable diamines dicarboxylic acids and amino-carboxylic acids foruse as amide-forming monomers, we may mention polymethylene diaminescontaining at least one hydrogen atom attached to each nitrogen atom,especially diprimary diamines, e. g. tetramethylene diamine,pentamethylene diamine, hexamethylene diamine and decamethylene diamine,glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid,sebacic acid, p-phenylene diacetic acid, terephthalic acid and the like,and G-aminocaproic acid (or its lactam) 7-amino-heptoic acid,Q-amino-nonanoic acid and the like. These substances are also examplesof reagents which may be employed for producing polyamides which mayserve as starting materials for the process of the present invention.

The following examples illustrate the invention but are not to beconsidered as limiting it in any way. In particular it is noted thatsmall changes in the conditions of the production of the originalpolymer or of the polymerisation described therein may make substantialdifferences to the properties of the products.

Example 1 Equal parts by weight of hexamethylene diammonium adipate andof a polyaminotriazole prepared from sebacic dihydrazide and having areactants. The heating was carried out for 1 Example 2 Equal parts byweight oi hexamethylcne diammonium adipate and a polyaminotriazoleformed from sebacic dihydrazide and having an intrinsic viscosity of 0.3were heated, as described in Example 1, in metacresol for 2 hours at210-220 C. under nitrogen. The resulting solution was precipitated bypouring into acetone, as described in Example 1. The resulting polymerwas white, tough and semi-fibrous, had a melting point of 227-330 C. andwas capable of yielding long fine filaments. It had intrinsic viscosityand nitrogen content respectively about 0.6

and 17.3%. On hydrolysis with hydrochloric acid, the amide-formingconstituents were split oil and the resulting regeneratedpolyaminotriazole had an intrinsic viscosity of about 0.5, compared withan intrinsic viscosity of 0.3 of the starting material. The solubilityproperties of the copolyamideaminotriazole were the same as those. givenin Example 1.

Example 3 A mixture of 1 molecular proportion of hexamethylenediammonium adipate and 1 molecular proportion of adipic acid was heatedin the melt under nitrogen for an hour at 200 C. Water was evolved andthe product was a white brittle mass, melting point 137140 C., insolublein water and acetone, and soluble in hot methanol. This body is referredto below as the Intermediate A."

225 parts by weight of a polyaminotriazole prepared from sebacicdihydrazide having an intrinsic viscosity of 0.3 were mixed with 37parts by weight of Intermediate A in an amount of metacresol equal tothe combined weight of the reactants. The mixture was heated for 4 hoursat 210 C. under nitrogen, and the resulting polymer precipitated asdescribed in Example 1. The polymer was a white semi-fibrous mass,having a melting point 195 'C., and it possessed very good fibre-formingproperties. It was insoluble in water and acetone, slowly soluble inboiling methanol and soluble in cold metacresol and formic acid. It hadan intrinsic viscosity of about 0.65. The polyaminotriazole regeneratedfrom the above copolymer as described in Example 2 had an intrinsicviscosity of about 0.59.

Example 4 62 parts by weight of polyaminotriazole prepared from adipicdihydrazide and having an intrinsic viscosity of 0.15 were heated with37.2 parts by weight 01 Intermediate A (see Example 3) in an amount ofmetacresol equal to the combined weight of the reactants. The heatingwas carried out for 2 hours at 220 C. under nitrogen, and the polymerprecipitated in excess acetone, re-dissolved in cold formic acid andprecipitated by pouring into excess alkali. The product, which was awhite, somewhat plastic mass, readily formed filaments and had anintrinsic viscosity of about 0.55. It was soluble in methanol, cresoland formic acid, and insoluble in acetone. The intrinsic viscosity ofthe polyaminotriazole regenerated from the copolymer was about 0.40.

Example 5 90 parts by weight of hexamethylene diammonium adipate andparts by weight of a polyaminotriazole prepared from adipic dihydrazidehaving an intrinsic viscosity of 0.32 and a melting point of about305310 C. were heated together in an amount of meta-cresol equal to thecombined weight of the reactants for a period of 3 hours at 210220' C.under nitrogen. The

- product was a white fibrous mass of melting point 250-255 0.,insoluble in water, acetone, and methanol. soluble in cresol and formicacid, had an intrinsic viscosity of about 0.8 and was capable of forminglong fine filaments.

Example 6 Example 5 was repeated using an polyaminotriazoleprepared fromsebacic dihydrazide and having an intrinsic viscosity of 0.3. Here theproduct had similar properties to the product of Example 5. but itsmelting point was 240-245 C.

Example 7 A polyaminotriazole was prepared by heating 200 parts byweight sebacic dihydrazide and 41 parts by weight of 50% aqueoushydrazine hydrate in an autoclave for hour at 240 C. and a maximumpressure of 600 lbs. per square inch. The product (Intermediate B") wasa granular, white solid of melting point 235 C., without fibreformingproperties, and of intrinsic viscosity 0.17.

50 parts by weight of Intermediate B and 50 parts by weight ofhexamethylene diammonium' adipate were heated under nitrogen for 2 hoursat 210 C. in an amount of metacresol equal to the combined weight of thereactants. The resulting polymer was precipitated as described inExample 1. It was a tough, white, fibrous mass (melting point, intrinsicviscosity and nitrogen content respectively about 174 C., 0.9 and 19.6%)from which in the molten state good fibres could be drawn. It wasinsoluble in water, acetone and methanol, and soluble in cresol andformic acid. On hydrolysis as described in Example 2, a polymer ofintrinsic viscosity 0.27 was regenerated.

Example 8 A polyaminotriazole, prepared from sebacic dihydrazide, wasfinely ground and refluxed in concentrated hydrochloric acid for 3hours. The resulting oily hydrochloride was separated, washed with waterand treated with a slight excess of aqueous ammonia to release thepolymeric base, which was washed with hot water and dried to yield apowder (Intermediate C) of melting point about 282 C. and intrinsicviscosity about 0.22. The powder was a polyaminotriazole having terminalcarboxyl groups.

parts by weight of Intermediate C was heated with 10 parts by weight oihexamethylene diamine under nitrogen for 4 hours at 210 C. in 100 partsof metacresol. The resulting polymer, precipitated as described inExample 1, was a brittle mass capable of forming good filaments from themelt (melting point, intrinsic viscosity and nitrogen contentrespectively about C.,.

0.66 and 23.1%). It was insoluble in water and acetone, and soluble inhot methanol cresol and formic acid. Hydrolysis as in Example 2regenerated a polymer of intrinsic viscosity about 0.24.

Example 9 A polyamide was produced by heating a mixture of 2 molecularproportions of hexamethylene diammonium adipate and 0.2 molecularproportion of adipic acid under a nitrogen for 5 hours at ZOO-210 C. inan amount of metacresol equal to the combined weight of the reactants,the resulting solution being poured into a large excess of acetone toprecipitate the polymer (Intermediate D"), which had melting point238-240 C.

amass? fibre-forming properties.

50 parts by weight of Intermediate-D and 50 parts by-weight ofIntermediate B (see Example.

combined weight of the reactants. The fibrous mass obtained onprecipitation of the resulting solution as described in Example 1 wascapable of yielding fine filaments of good strength and properties.

30 parts by weight of Intermediate F and 30 parts by weight ofIntermediate D (see Example 9) were heated under nitrogen for 4 hours at'1) were heated to e r u r nitrogen for 4 5 extension (melting point220-225 C., intrinsic hours at 210: c.inau amou t ofmtacrescl equalviscosity about 0.69, nitrogen content about to the combin wei h of treactants. and the 21.2%). It was insoluble in water and acetone,product. precipi ted as described in Example very slightly soluble inmethanol, and soluble in The resulting polymer was a white, fibrousmass, cresol a formic acid of melting point, intrinsic viscosity andnitrogen. 1 content respectively about 184 C., 0.61 and 16.2221, Example12 and yielded. from the melt fibre.s.having g A mixture of 100molecular proportion of hexaf g fg f'fig g gg 22253 g g gg methylenediammonium adipate and 10.5 molece s folysis of this polymer by themethod described 15 if g m i i of hefiamgtgylene s fi g f le 2regenerated a polymer of intrinsic e o en or ours a 10 C. m g t 0 29 inan amount of metacresol equal to the combined S6051 ya u weight of thereactants. The solution obtained Example 10 was precipitated by pouringinto excess acetone E uimolecular proportions of hexamethylene 0 and e Puc found to e o e y 1 d (Indiar monium adipate and adipic acid were dis-2 termeqlate G l m point, intrinsic viscosity solved in water nd thesolution heated under and mtrosen nten r sp ti y a t 2 0. nitrogen for 1hours at 200-2l0 C., during 02'! and 12.3%. W fi had o fi er DX D- whichtime the water was rapidly distilled off. erties. On cooling, a white,brittle solid was obtained, 60 parts by weight of Intermediate G and 40and this was extracted with ether to remove unparts by weight ofIntermediate F (see Example changed adipic acid and then with methanolto 11) were heated under nitrogen for 6 hours at dissolve the fraction(Intermediate E"), which 200-2l0 C. in an amount of metacresol equal towas shown to be N.N-diadipyl-hexamethylene the combined weight of thereactants. After prediamine, melting point 176 0., equivalent weight 30cipitation as described in Exampl 1 a, semi- '189 (theory 186) nitrogencontent about 7.6% fibrous mass was obtained, having melting point(theory 7 53%). 220-225 C., intrinsic viscosity about 0.45, nitro- 50parts y we t f Intermediate B (see gen content about 19.5%, and goodfibre-forming a p and 5 parts y Weight of Intermediate properties. Itssolubility properties were similar E were heated under nitrogen for 3hours at 210 to those given in Example C. in an amount of metacresolequal to the combined weight of th reactants, and the produfg Example 13precipitated as described in Example 1 Hexamethylene diamrnonium adipatewas white'.sem.l'fibmus .mass of meltmg mixed with various proportionsof a. polyaminotrinsic viscosity and mtrogen content respectively 40triazole (intrinsic b t bout 205 0. 0.56 and 22.2%. The mass could 9 Y aprepined from sebacic dihydrazide, and heated under nitrobe melt-spun togive fine filaments of good v o strength and extension. Its solubilityproperties gen for 3 hours at 210 an amount of meta" were Similar tothose given in Example cresol equal to the combined weight of theredrolysis of the product by the method described f The resultmg werePoured in Example 2 regenerated a polymer of intrinsic into excessacetone, the precipitates red ssolved viscosity about 021 in formic acidand reprecipitated by pouring into dilute aqueous alkali, and theproducts washed Exa p 11 free from salts and dried. The proportions ofre- A polyaminotriazole was prepared by heating actants and theproperties of the products are 150 parts by weight of adipic dihydrazideand 30 shownin the following table:

$233 33 Polyamino- Product ge g 333%, iit wati weight ttlf t. tiittii?98 2 Fibrous mass (rather hard)" 250-252 about 0.77 95 5 Soft fibrousmass about240 about 0.90 90 10 do about222 about 0.69 50 50 Powderysolidabout200 about 0.5?

parts by weight of 50% aqueous hydrazine hy- All the products had verygood fibre-forming drate in an autoclave for 1 hour at 200 C. andproperties and had solubility properties similar a maximum pressure of220 lbs. per square inch. to those given in Example 7. The product was asticky, white mass which was Exam 1e 14 washed with cold water and driedto yield a white powder (Intermediate F) of melting point 215- 143 partsby weight of a triazole bis-Valerie 220 C., intrinsic viscosity about0.10, and nitrogen acid, prepared as described above, and 58 partscontent about 34.8%, which had no fibre-forming by weight ofhexamethylene diamine were heated under nitrogen for 5 hours at 210 C.in an amount of metacresol equal to the combined weight of thereactants. A polymer was precipitated from the resulting solution asdescribed 210 C. in an amount of metacresol equal to the in Example 1and, after washing and drying, was

found to have a melting point above 280 0., softening point about 170 C.and nitrogen content about 19.1%, and to yield filaments from the melt.It was insoluble in acetone, fairly soluble in methanol, and soluble inhot water, cresol and formic acid.

Example 15 Two molecular proportions of hexamethylene diamine werecondensed with one molecular proportion of adipic diester to yield thesubstance NH2.(CH2) s.NH.CO.(CH2) 4.CO.NH.(CH2) c.NH2

("Intermediate H).

10 parts by weight of Intermediate H and 20 parts by weight of thepolyaminotriazole of Example 13 were heated under nitrogen for 10minutes at 260 C. to produce a clear melt, and the temperature was thenallowed to fall to 220 C.

over 4 hour while the pressure was reduced to in the past been applied.Generally the products have an aillnity for the dispersed insoluble typeof dyes'tufl now generally applied to cellulose formin film-forming orlacquer substances or other ingredients, for example cellulose acetate,

aceto-butyrate and aceto-stearate, ethyl cellulose,

5 mm. After about minutes, resolidification commenced, and thetemperature was raised to 240 C. and maintained for 1 hour. The cooledproduct was an opaque, fairly tough mass, melting point 225-230 andnitrogen content about 20.6%. Its solubility properties were similar tothose given in Example '7. Good filaments, which could be cold-drawn,were obtainable from the melt.

Example 16 20 parts by weight of Intermediate H (see Example 15) and 30parts by weight of a poly aminotriazole (intrinsic viscosity about0.17), prepared from adipic dihydrazide, were heated under nitrogen for10 minutes at 260 C. to produce a clear melt, and then maintained at250- 260 C. and 5 mm. pressure for minutes. On cooling, a hard, brittle,glassy polymer was obtained, which had melting point 210-215" C..andintrinsic viscosity about 0.62, and which yielded filaments from themelt. It was, insoluble in water and acetone, and soluble in boilingmethanol, cresol and formic acid.

The invention includes the production of filaments, films and otherarticles from the polymers produced as described above. Generally themost suitable method of producing filaments is by melt spinning, i. e.by extruding a melt of the polymer through suitable orifices. In generalthe temperature of the polymer to be extruded should be some 10-30 abovethe melting point of the polymer. This melting temperature may bemodified to some extent, e. g. with a view to reducing any tendency todecomposition during spinning at very high temperatures, by mixing thepolymer with suitable proportions of plasticisers, for examplesulphonamide plasticisers, phenolic plasticisers, urea and thioureaplasticisers. Such plasticisers may either be left in the products ormay be partially or completely extracted therefrom. Filaments may alsobe produced by wet or dry spinning methods from solutions in suitablesolvents, for example formic acid or acetic acid or the phenolicsolventsreferred to above.

The filaments so formed may, if the polymer be of suiiiciently highmolecular weight, be drawn out at comparatively low temperatures, oreven at atmospheric temperature, to very fine filaments having hightenacity and good elasticity. The resulting filaments may then be usedfor any of the purposes to which artificial silks have oxyethylcellulose, oxyethyl cellulose acetate, benzyl cellulose and othercellulose derivatives, plasticisers or softening agents, dyestuffs,pigments and the like. It will be noted that in Examples 1 to 14 thepolymerization is carried out with the reagents in solution, and inExamples 15 and 16 with the reagents in the molten state. The expressionliquid phase" is used in the claims to connote that the reagents aremolten or in solution in a liquid solvent.

Having described our invention, what we desire to secure by LettersPatent is:

1. Process for the production of synthetic linear polymers from a linearpoly-1.2.4-triazole,

, which is obtained by heating a reaction mixture,

which on complete hydrolysis contains a mixture.

of a dicarboxylic acid free from reactive groups other than the carboxygroups and a base selected from the group consisting of hydrazine andmixtures of hydrazine and ammonia, when hydrazine is the base therebeing present more than 2 m 'les of hydrazine for each mole ofdicarboxylic cid, the excess of hydrazine above 2 moles for each mole ofdicarboxylic acid being in amount suflicient to produce a polymerresistant to hydrolysis by hydrochloric acid, and when a mixture ofhydrazine and ammonia is the base there being present more than 2 molesof hydrazine and ammonia together for each mole of dicarboxylic acid andmore than 1 mole of hydrazine for each mole of dicarboxylic acid, theexcess of hydrazine and ammonia above 2 moles for each mole ofdicarboxylic acid and the excess of hydrazine above 1 mole for each moleof dicarboxylic acid being in an amount sufficient to produce a polymerresistant to hydrolysis by hydrochloric acid, which comprises heatingsaid poly-1.2.4-triazole with a bifunctional carboxylic-amide-formingsubstance containing functional groups complementary to terminal groupsof said poly-1.2.4- triazole and selected from the group consisting ofdiamines, dicarboxylic acids, monoaminomonocarboxylic acids andcarboxylic-amideforming derivatives thereof having at least one hydrogenatom attached to the nitrogen of each amino group and free from reactivegroups other than the carboxylic-amide-forming groups, the reactionbeing carried out with the reaction mass in the liquid phase and beingterminated whileit is still liquid.

2. Process for the production of synthetic linear polymers from a linearpoly-1.2.4-triazole base there being present more than 2 moles oihydrazine for each mole of dicarboxylic acid, the excess of hydrazineabove 2 moles for each mole of dicarboxyllc acid being in amountsuflicient t produce a polymer resistant to hydrolysis by hydrochloricacid, and when a mixture of hydrazine and ammonia is the base therebeing present more than 2 moles of hydrazine and ammonia together foreach mole oi. dicarboxylic acid and more than 1 mole of hydrazine foreach mole of dicarboxylic acid, the excess of hydrazine and ammoniaabove 2 moles for each mole oi dicarboxylic acid and the excess ofhydrazine above 1 mole for each mole oi. dicarboxylic acid being in anamount sufllcient to produce a polymer resistant to hydrolysis byhydrochloric acid, which comprises heating said poly-l.2.4-triazole witha biiunctional carboxylic-amide-iforming substance containing functionalgroups complementary to terminal groups of said poly-1.2.4- triazole andselected from the group consisting of diamines, dicarboxylic acids,monoaminomonocarboxylic acids and carboxylic-amideforming derivativesthereof having at least one hydrogen atom attached to the nitrogen ofeach amino group and free from reactive groups other than thecarboxylic-amide-iorming groups, the reaction being carried out with thereaction mass in the liquid phase and being terminated while it is stillliquid.

3. Process for the production of synthetic linear polymers from a linearpoly-4-amino-L2u4-triazole, which is obtained by heating a reactionmixture, which on complete hydrolysi contains a mixture of adlcarboxylic acid free from reactive groups other than the carboxygroups and hydrazine, there being present more than 2 moles of hydrazinefor each mole of dicarboxylic acid, the excess of hydrazine above 2moles for each mole of dicarboxylic acid being in amount suincient toproduce a polymer resistant to hydrolysis by hydrochloric acid, whichcomprises heating said poly-4-amino-1.2.4-triazole with a bitunctionalcarboxylic-amide-forming substance containing functional groupscomplementary to terminal groups of said poly-4-amino-1.2.4-triazole andselected from the group consisting of diamines, dicarboxylic acids,monoamino-monocarboxylic acids and carboxylic-amide-iorming derivativesthereof having at least one hydrogen atom attached to the nitrogen ofeach amino group and free from reactive groups other than thecarbcxylic-amide-forming groups, the reaction being carried out with thereaction mass in the liquid phase and being terminated while it is stillliquid.

4. Process for the production of synthetic linear polymers from a linearpoly-i-amino-LZA-triazole of intrinsic viscosity up to 0.9, which isobtained by heating a reaction mixture, which on complete hydrolysiscontains a mixture of a dicarboxylic acid free from reactive groupsother than the carboxy groups and hydrazine, there being present morethan 2 moles of hydrazine for each mole of dicarboxylic acid, the excess01' hydrazine above 2 moles for each mole of dicarboxylic acid being inamount suflicient to pro duce a polymer resistant to hydrolysis byhydrochloric acid, which comprises heating said poly4-amino-l.2.4-triazole with a bifunctional carboxylic amide formingsubstance containing 12 acids and carboxylic-amide-iorming derivativesthereoi having at least one hydrogen atom attached to the nitrogen ofeach amino group and free from reactive groups other than thecarboxylic-amide-forming groups, the reaction being carried out with thereaction mass in the liquid phase and being terminated while it is stillliquid.

5. Process for the production of synthetic linear polymers from a linearpoly-1.2.4-triazole, which is obtained by heating a reaction mixture,which on complete hydrolysis contains a mixture of a dicarboxylic acidfree from reactive groups other than the carboxy groups and a baseselected from the group consisting of hydrazine and mixtures ofhydrazine and ammonia, when hydrazine is the base there being presentmore than 2 moles of hydrazine for each mole of dicarboxylic acid, theexcess of hydrazine above 2- moles for each mole of dicarboxylic acidbeing in amount willcient to produce a polymer resistant to hydrolysisby hydrochloric acid, and when a mixture of hydrazine and ammonia is thebase there being present more than 2 moles of hydrazine and ammoniatogether for each mole of dicarboxylic acid and more than 1 mole ofhydrazine for each mole of dicarboxylic acid, the excess of hydrazineand ammonia above 2 moles for each mole of dicarboxylic acid and theexcess of hydrazine above 1 mole for each mole of dicarboxylic acidbeing in an amount suilicient to produce a polymer resistant tohydrolysis by hydrochloric acid, which comprises heating saidpoly-1.2.4-triazole with a biiunctional carboxylic-amide-forming linearpolycarboxylamide containing two terminal amino groups complementary toterminal groups of said poly-1.2.4-triazole and free from reactivegroups other than the carboxylic-amideforming groups, there being atleast one hydrogen atom attached to the nitrogen of each amino group,the reaction being carried out with the reaction mass in the liquidphase and being terminated while it is still liquid.

6. Process for the production oi synthetic linear polymers from a linearpoly-1.2.4-triazole of intrinsic viscosity up to 0.9, which i obtainedby heating a reaction mixture, which on complete hydrolysis contains amixture 01 a dicarboxylic acid free from reactive groups other than thecarboxy groups and a base selected from the group consisting ofhydrazine and mixtures of hydrazine and ammonia, when hydrazine is thebase there being present more than 2 moles of hydrazine for each mole ofdicarboxylic acid, the excess of hydrazine above 2 moles for each moleof dicarboxylic acid being in amount sufiieient to produce a polymerresistant to hydrolysis by hydrochloric acid, and when a mixture ofhydrazine and ammonia is the base there being present more than 2 molesof hydrazine and ammonia together for each mole of dicarboxylic acid andmore than 1 mole of hydrazine for each mole of dicarboxylic acid, theexcess of hydrazine and ammonia above 2 moles for each mole ofdicarboxylic acid and the excess of hydrazine above 1 mole for each moleof dicarboxylic acid being in an amount suflicient to produce a polymerfunctional groups complementary to terminal groups of saidpoly-4-amino-1.2.4-triazole and selected from the group consisting ofdiamines, dicarboxylic acids, monoamino-monocarboxylic resistant thydrolysis by hydrochloric acid, which comprises heating saidpoly-1.2.4-triazole with a bifunctional carboxylic-amide-forming linearpolycarboxylamide containing two terminal amino groups complementary toterminal groups of said poly-1.2.4-triazole and free from reactivegroups other than the carboxylic-amideforming groups, there being atleast one hydroen atom attached to the nitrogen of each amino 13 gnup,the reaction being carried out with the reaction mass in the liquidphase and being terminated while it is still liquid.

'7. Process for the production of synthetic linear condensation polymersfrom a linear poly- 4-amino-1.2-.4-triazole, which is obtained byheating a reaction mixture containing a dihydrazide of a polymethylenedicarboxylic acid free from reactive groups other than the carboxygroups with sufiicient hydrazine to produce a polymer resistant tohydrolysis by boiling hydrochloric acid, which comprises heating saidpoly- 4-amino-1.2.4-triazole with a bifunctional carboxylic amideforming substance containing functional groups complementary to terminalgroups of said poly-4-amino-l.2.4-triazole and selected from the groupconsisting of diamines, dicarboxylic acids, monoamino-monocarboxylicacids and ca'rboxylic-amide-forming derivatives thereof having at leastone hydrogen atom attached to the nitrogen 01' each amino group and freefrom reactive groups other than the carboxylic-amide-forming groups, thereactionbeing carried out with the reaction mass in the liquid phase andbeing terminated while it is still liquid.

8. Process for the production of synthetic linear condensation polymersfrom a linear poly- 4-amino-1.2.4-triazole of intrinsic viscosity up to0.9, which is obtained by heating a reaction mixture containing adihydrazide of a polymethylene dicarboxylic acid free from reactivegroups other than the carboxy groups with sufllcient hydrazine toproduce a polymer resistant to hydrolysis b" boiling hydrochloric acid,which comprises heating said poly-4-amino-1.2.4-triazole with abifunctional carboxylic-amide-iorming substance containing functionalgroups complementary to terminal groups of saidpoly-4-amino-l.2.4-triazole and selected from the group consisting ofdiamines, dicarboxylic acids, monoamino-monocarboxylic acids andcarboxylic-amide-i'ormin derivatives thereof having at least onehydrogen atom attached to the nitrogen of each amino group and free fromreactive groups other than the carboxylic-amide-forming groups, thereaction being carried out with the reaction mass in the liquid phaseand being terminated while it is still liquid.

9. Process for the production of synthetic l near polymers from a linearpoly-1.2.4-tria2ole, which is obtained by heating a reaction mixture,which on complete hydrolysis contains a mixture of a polymethylenedicarboxylic acid free from reactive groups other than the carboxygroups and a base selected from the group consisting of hydrazine andmixtures of hydrazine and ammonia, when hydrazine is the base there beinpresent more than 2 moles of'hydrazine for each mole of dicarboxylicacid, the excess of hydrazine above 2 moles for each mole ofdicarboxylic acid being in amount suificient to produce a polymerresistant to hydrolysis by hydrochloric acid, and when a mixture ofhydrazine and ammonia is the base there being present more than 2 molesof hydrazine and ammonia together for each mole of dicarboxylic acid andmore than 1 mole of hydrazine for each mole of dicarboxylic acid, theexcess of hydrazine and ammonia above 2 moles for each mole ofdicarboxylic acid and the excess of hydrazine above 1 mole for each moleof dicarboxylic acid being in an amount suflicient to produce a polymerresistant to hydrolysis by hydrochloric acid. which comprises heatingsaid -poly-1.2.4-triazole with a bifunctional carboxylicamide-formingsubstance containing functional groups complementary to terminal groupsat said poly-1.2.4-triazole and selected from the troup consisting ofdiamines, dicarboxylic acids, monoamino-monocarboxylic acids andcarboxylicamide-Iorming derivatives thereof having at least one hydrogenatom attached to the nitrogen of each amino group and free from reactivegroups otherthan the carboxylic-amide-forming groups, the reaction beingcarried out with the reaction mass in the liquid phase and beingterminated while it is still liquid.

10. Process for the production of synthetic linear polymers from alinear poly-1.2.4-triazole, which is obtained by heating a reactionmixture, which on complete hydrolysis contains a mixture of adicarboxylic acid free from reactive groups other than the carboxygroups and a base selected from the group consisting of hydrazine andmixtures of hydrazine and ammonia, when hydrazine is the base therebeing present more than 2 moles of hydrazine for each mole oi!dicarboxylic acid, the excess of hydrazine above 2 moles for each moleof dicarboxylic acid being in amount sufficient to produce a polymerresistant to hydrolysis by hydrochloric acid, and when a, mixture ofhydrazine and ammonia is the base there being present more than 2 molesof hydrazine and ammonia together for each mole of dicarboxylic acid andmore than 1 mole of hydrazine for each mole of dicarboxylic acid, theexcess of hydrazine and ammonia above 2 moles for each mole ofdicarboxylic acid and the excess of hydrazine above 1 mole for each moleof dicarboxylic acid being in an amount sufllcient to produce a polymerresistant to hydrolysis by hydrochloric acid, which comprises heatingsaid poly-1.2.4-triazole with a bifunctional carboxylic-amide-Iorminglinear polycarboxylamide containing two terminal amino groupscomplementary to terminal groups of said poly-1.2.4-triazole and freefrom reactive groups other than the carboxylic-amideforming groups,there being at least one'hydrogen atom attached to the nitrogen of eachamino group, said polycarboxylamides being the condensation products ofpolymethylene diamines with polymethylene dicarboxylic acids, thereaction being carried out with the reaction mass in the liquid phaseand being terminated while it is still liquid.

11. Process for the producton of synthetic linear polymers from a linearpoly-1.2.4-triazole, which is obtained by heating a reaction mixture,which on complete hydrolysis contains a mixture of a polymethylenedicarboxylic acid free from reactive groups other than the carboxygroups and a base selected from the group consisting of hydrazine andmixtures of hydrazine and ammonia, when hydrazine is the base therebeing present more than 2 moles of hydrazine for each mole ofdicarboxylic acid, the excess of hydrazine above 2 moles for each moleof dicarboxylic acid being in amount suflicient to produce a polymerresistant to hydrolysis by hydrochloric acid, and when a mixture ofhydrazine and ammonia is the base there being present more than 2 molesof hydrazine and ammonia together for each mole of dicarboxylic acid andmore than 1 mole of hydrazine for each mole of dicarboxylic acid, theexcess of hydrazine and ammonia above 2- moles for each mole ofdicarboxylic acid and the excess of hydrazine above 1 mole for each moleof dicarboxylic acid being in an amount suflicient to produce a polymerresistant to hydrolysis by hydrochloric acid, which comprises heatingsaid poly-1.2.4-triazole with a bifunctional carboxylicamide-forminglinear polycarboxylamide containing two terminal amino groupscomplementary to terminal groups 0! said poly-1.2.4- triazole and treefrom reactive groups other than the carboxylic amide-forming groups,there being 5 at least one hydrogen atom attached to the nitrogen ofeach amino group, said polycarboxylamides being the condensationproducts of polymethylene diamines with polymethylene dicarboxylicacids, the reaction being carried out with the reaction mass in theliquid phase and being terminated while it is still liquid.

JAMES WO'I'HERSPOON FISHER.

EDWARD WIILIAM WHEATIEY.

16 REFERENCES CITED The following references are of record in the fileof this patent:

UNITED STATES PATENTS Number Name Date 2,332,303 DAlelio Oct. 19, 19432,349,979 Moidenhauer et a1. May 30, 1944 2,395,642 Priehard Feb. 26,1946

1. PROCESS FOR THE PRODUCTION OF SYNTHETIC LINEAR POLYMERS FROM A LINEARPOL-1.2.4-TRIAZOLE, WHICH IS OBTAINED BY HEATING A REACTION MIXTURE,WHICH ON COMPLETE HYDROLYSIS CONTAINS A MIXTURE OF A DICARBOXYLIC ACIDFREE FROM REACTIVE GROUPS OTHER THAN THE CARBOXY GROUPS AND A BASESELECTED FROM THE GROUP CONSISTING OF HYDRAZINE AND MIXTURES OFHYDRAZINE AND AMMONIA, WHEN HYDRAZINE IS THE BASE THERE BEING PRESENTMORE THAN 2 MOLES OF HYDRAZINE FOR EACH MOLE OF DICARBOXYLIC ACID, THEEXCESS OF HYDRAZINE ABOVE 2 MOLES FOR EACH MOLE OF DICARBOXYLIC ACIDBEING IN AMOUNT SUFFICIENT TO PRODUCE A POLYMER RESISTANT TO HYDROLYSISBY HYDROCHLORIC ACID, AND WHEN A MIXTURE OF HYDRAZINE AND AMMONIA IS THEBASE THERE BEING PRESENT MORE THAN 2 MOLES OF HYDRAZINE AND AMMONIATOGETHER FOR EACH MOLE OF DICARBOXYLIC ACID AND MORE THAN 1 MOLE OFHYDRAZINE FOR EACH MOLE OF DICARBOXYLIC ACID, THE EXCESS OF HYDRAZINEAND AMMONIA ABOVE 2 MOLES FOR EACH MOL OF DICARBOXYLIC ACID AND THEEXCESS OF HYDRAZINE ABOVE 1 MOLE FOR EACH MOLE OF DICARBOXYLIC ACIDBEING IN AN AMOUNT SUFFICIENT TO PRODUCE A POLYMER RESISTANT TOHYDROLYSIS BY HYDROCHLORIC ACID, WHICH COMPRISES HEATING SAIDPOL-1.2.4-TRIAZOLE WITH A BIFUNCTIONAL CARBOXYLIC-AMIDE-FORMINGSUBSTANCE CONTAINING FUNCTIONAL GROUPS COMPLEMENTARY TO TERMINAL GROUPSOF SAID POL-1.2.4TRIAZOLE AND SELECTED FROM THE GROUP CONSISTING OFDIAMINES, DICARBOXYLIC ACIDS, MONAMINOMONOCARBOXYLIC ACIDS ANDCARBOXYLIC-AMIDEFORMING DERIVATIVES THEREOF HAVING AT LEAST ONE HYDROGENATOM ATTACHED TO THE NITROGEN OF EACH AMINO GROUP AND FREE FROM REACTIVEGROUPS OTHER THAN THE CARBOXYLIC-AMIDE-FORMING GROUPS, THE REACTIONBEING CARRIED OUT WITH THE REACTION MASS IN THE LIQUID PHASE AND BEINGTERMINATED WHILE IT IS STILL LIQUID.